FR2506300A1 - Bromo-poly:fluoro alkyl phenyl ether(s) - intermediates for pharmaceuticals and plant protection agents are prepd. by reacting the phenate with di:bromo-poly:fluoro-methane or ethane - Google Patents

Bromo-poly:fluoro alkyl phenyl ether(s) - intermediates for pharmaceuticals and plant protection agents are prepd. by reacting the phenate with di:bromo-poly:fluoro-methane or ethane Download PDF

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FR2506300A1
FR2506300A1 FR8110319A FR8110319A FR2506300A1 FR 2506300 A1 FR2506300 A1 FR 2506300A1 FR 8110319 A FR8110319 A FR 8110319A FR 8110319 A FR8110319 A FR 8110319A FR 2506300 A1 FR2506300 A1 FR 2506300A1
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Prior art keywords
formula
phenate
bromo
fluorohaloethyl
poly
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FR2506300B1 (en
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Isabelle Rico
Claude Wakselman
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Rhone Poulenc Specialites Chimiques
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Rhone Poulenc Specialites Chimiques
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Priority to DE8181401771T priority patent/DE3166515D1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Bromo-polyfluoro-alkyl ethers of formula R-substd.-phenyl- O-(CF2)n-Br (I) are new (where n is 1 or 2; R is one or more gps. chosen from H, 1-12C alkyl, phenyl, 1-12C alkoxy, phenoxy, NO2, CN, halo, CF3, -CONR1R2 and -NR1R2 and R1, R2 are H or 1-6C alkyl). (I) are intermediates for the prepn. of plant protection agents and pharmaceuticals, esp. by halogen exchange to form the perfluoroalkyl ether intermediates.

Description

NOUVEAUX FLUOROHALOETHYLETHERS ARONATIQUES
ET LEUR PROCEDE DE PREPARATION
La présente invention a pour objet de nouveaux fluorohaloéthyléthers aromatiques. L'lnvention concerne également un procédé de préparation de ces composés.NEW ARONATIC FLUOROHALOETHYLETHERS
AND THEIR PREPARATION PROCESS
The present invention relates to new aromatic fluorohaloethyl ethers. The invention also relates to a process for the preparation of these compounds.

Les nouveaux composés aromatiques selon la présente invention ont pour formule générale

Figure img00010001

dans laquLI1 :
- X1 et X2 identiques ou différents représentent F ou C1
- X3 représente Br ou I
- et R représente au moins un élément choisi parmi le groupe comprenant l'hydrogène, les radicaux alkyle ayant de 1 à 12 atomes de carbone, le radical phényle, les radicaux alkoxy ayant de 1 à 12 atomes de carbone, le radical phényloxy et les radicaux NO2, CN, F,
C1, Br, I, CF3, CONR R et NR1R2 ou R1 et R2 identiques ou différents representent chacun un hydrogene ou un radical alkyle ayant de 1 a 6 atomes de carbone.The new aromatic compounds according to the present invention have the general formula
Figure img00010001

in laquLI1:
- X1 and X2 identical or different represent F or C1
- X3 represents Br or I
- And R represents at least one element chosen from the group comprising hydrogen, the alkyl radicals having from 1 to 12 carbon atoms, the phenyl radical, the alkoxy radicals having from 1 to 12 carbon atoms, the phenyloxy radical and the NO2, CN, F radicals,
C1, Br, I, CF3, CONR R and NR1R2 or R1 and R2, which are identical or different, each represent a hydrogen or an alkyl radical having from 1 to 6 carbon atoms.

L'invention concerne plus particulierement les composés de formule I dans laquelle X1 et X2 représentent F, X3 et R ayant la signification précédente. The invention relates more particularly to the compounds of formula I in which X1 and X2 represent F, X3 and R having the above meaning.

L'invention concerne encore plus particulièrement les composés de formule I dans laquelle X1 et X2 représentent F et X3 représente
Br, R ayant la signification précédente.The invention relates more particularly to the compounds of formula I in which X1 and X2 represent F and X3 represents
Br, R having the previous meaning.

Les composés de formule I ont un grand intérêt industriel dans la mesure où ils peuvent être utilisés en tant qu'intermédiaires de synthèse pour la préparation de produits ayant une activité phytosanitaire ou pharmaceutique. The compounds of formula I are of great industrial interest insofar as they can be used as synthesis intermediates for the preparation of products having phytosanitary or pharmaceutical activity.

L'invention concerne également un procédé pour la préparation des composés de formule I caractérisé en ce que l'on fait réagir le composé de formule : X4-CFX1-CFX2-X3 (II) avec un phénate de formule

Figure img00010002

où X X2, X3 et R ont la signification précédente et M+ représente un cation dérivé d'un métal alcalin, et X4 représente C1, Br ou I dans un solvant aprotique polaire anhydre en présence d'un thiol agissant comme initiateur de la réaction.The invention also relates to a process for the preparation of the compounds of formula I characterized in that the compound of formula: X4-CFX1-CFX2-X3 (II) is reacted with a phenate of formula
Figure img00010002

where X X2, X3 and R have the above meaning and M + represents a cation derived from an alkali metal, and X4 represents C1, Br or I in an anhydrous polar aprotic solvent in the presence of a thiol acting as initiator of the reaction.

Lorsque l'on veut obtenir un composé de formule I dans laquelle
X3 est I, on peut utiliser comme produit de départ un composé de formule II dans laquelle X3 est I et X4 est I, Br ou C1.When we want to obtain a compound of formula I in which
X3 is I, it is possible to use as starting material a compound of formula II in which X3 is I and X4 is I, Br or C1.

Lorsque l'on veut obtenir un compose de formule I dans laquelle
X3 est Br, il faut utiliser comme produit de départ un composé de formule II dans laquelle X3 est Br et X4 est soit Br soit C1.When we want to obtain a compound of formula I in which
X3 is Br, a compound of formula II must be used as the starting material in which X3 is Br and X4 is either Br or C1.

La demanderesse a constaté que pour atteindre les meilleurs rendements, il est préférable d'utiliser un phénate de potassium. The Applicant has found that to achieve the best yields, it is preferable to use a potassium phenate.

En effet, c'est lorsque ce dernier est utilisé que la quantité de produit secondaire (produit correspondant ayant le groupement
OCFX1CFX2H) formee est la plus faible.Indeed, it is when the latter is used that the quantity of secondary product (corresponding product having the grouping
OCFX1CFX2H) formed is the weakest.

Le solvant aprotique polaire mis en oeuvre est de préférence un solvant dont la constante diélectrique est supérieure à 15. On peut citer comme exemple de solvants convenant particulièrement bien è la mise en oeuvre du procédé de l'invention, le diméthyl- formamide, le diméthylacétamide, le diméthylsulfoxyde, l'hexaméthylène phosphorotriamide, le N-méthylpyrrolldone et le sulfolane. The polar aprotic solvent used is preferably a solvent whose dielectric constant is greater than 15. Mention may be made, as an example of solvents which are particularly suitable for carrying out the process of the invention, dimethylformamide, dimethylacetamide , dimethyl sulfoxide, hexamethylene phosphorotriamide, N-methylpyrrolldone and sulfolane.

Le solvant utilisé doit être aprotique pour éviter la formation du produit secondaire ayant le groupement O-CFX1-CFX2H et polaire pour exalter la réactivité du phénate.The solvent used must be aprotic to avoid the formation of the secondary product having the group O-CFX1-CFX2H and polar to enhance the reactivity of the phenate.

Selon un mode de réalisation tout particulièrement préféré, on utilise comme solvant le diméthylformamide.  According to a very particularly preferred embodiment, dimethylformamide is used as solvent.

Selon une caractéristique fondamentale du procédé selon l'invention, il est nécessaire pour initier la réaction, d'ajouter au milieu fractionnel un thiol. Ce thiol que l'on peut représenter par la formule R3SH libère, puisque l'on se trouve en milieu basique, l'ion R3S dont le caractère nucléophile permet
3 l'initiation. R3 peut représenter tout radical organique hydrocarboné (alkyle ou aryle) ou contenant des hétéroatomes. On peut citer comme exemples de thiols utilisables : les alcanethiols, comme l'éthanethiol, le propanethiol, le butanethiol, les thiophénols et les benzylmercaptans. On préfère utiliser le propanethiol car les produits secondaires dont il est responsable sont suffisamment volatils pour être éliminés facilement.Le thiol est utilise en quantité telle que le rapport molaire du thiol au phénate est compris entre environ 0,05 et environ 0,2. Encore plus préférentiellement, ce rapport est compris entre 0,07 et 0,15.According to a fundamental characteristic of the process according to the invention, it is necessary to initiate the reaction, to add to the fractional medium a thiol. This thiol which can be represented by the formula R3SH releases, since we are in basic medium, the ion R3S whose nucleophilic nature allows
3 initiation. R3 can represent any organic hydrocarbon radical (alkyl or aryl) or containing heteroatoms. Examples of usable thiols that may be mentioned include: alkanethiols, such as ethanethiol, propanethiol, butanethiol, thiophenols and benzylmercaptans. It is preferred to use propanethiol because the secondary products for which it is responsible are sufficiently volatile to be easily eliminated. The thiol is used in an amount such that the molar ratio of thiol to phenate is between approximately 0.05 and approximately 0.2. Even more preferably, this ratio is between 0.07 and 0.15.

On met en oeuvre de preference les composes II et III en quantité telle que le rapport molaire du composé II au phénate III est compris entre environ 1 et 5. Encore plus -préférentiellement, ce rapport est compris entre environ 1 et 3. Compounds II and III are preferably used in an amount such that the molar ratio of compound II to phenate III is between approximately 1 and 5. Even more preferably, this ratio is between approximately 1 and 3.

Le solvant est utilisé en quantité telle que le nombre de mole de phénate par litre de solvant est compris entre environ 0,1 et environ 0,5 et encore plus préférentiellement entre 0,15 et 0,3. The solvent is used in an amount such that the number of moles of phenate per liter of solvent is between approximately 0.1 and approximately 0.5 and even more preferably between 0.15 and 0.3.

On effectue généralement la réaction à une température comprise entre environ 20 et lOO0C et plus particulièrement entre 20 et 600C. The reaction is generally carried out at a temperature between about 20 and 100 ° C. and more particularly between 20 and 600 ° C.

On opère de préférence sous pression atmosphérique bien que des pressions supérieures ou inférieures ne soient pas exclues du domaine de l'invention. It is preferably carried out at atmospheric pressure although higher or lower pressures are not excluded from the scope of the invention.

Les temps de réaction nécessaires a l'accomplissement de la réaction selon l'invention peuvent varier dans de larges limites. The reaction times necessary for carrying out the reaction according to the invention can vary within wide limits.

Ils sont généralement compris entre 3 et 12 h.They are generally between 3 and 12 h.

La demanderesse a constaté que pour mettre en oeuvre le procedé selon l'invention dans de meilleures conditions, il était souhaitable d'utiliser un solvant bien dégazé, c'est-à-dire debarrassé de l'oxygène de l'air et de maintenir le milieu réactionnel sous agitation. The Applicant has found that in order to implement the process according to the invention under better conditions, it was desirable to use a solvent that is well degassed, that is to say rid of oxygen from the air and to maintain the reaction medium with stirring.

De plus, pour une bonne mise en oeuvre de l'invention, il convient d'utiliser un phénate exempt d'eau. De ce fait, il est recommande de sécher le phénate dans une étape préalable. En effet, la présence d'eau dans le milieu réactionnel favorise la formation du produit secondaire correspondant comportant le groupement O-CFX1-CFX2H.  In addition, for a good implementation of the invention, a water-free phenate should be used. Therefore, it is recommended to dry the phenate in a preliminary step. Indeed, the presence of water in the reaction medium promotes the formation of the corresponding secondary product comprising the group O-CFX1-CFX2H.

Les composés de formule Il et III sont préparés selon des techniques bien connues de l'homme de l'art. The compounds of formula II and III are prepared according to techniques well known to those skilled in the art.

L'invention va être maintenant plus complètement décrite à l'aide des exemples qui vont suivre. Ceux-ci ne sauraient être
interprétés comme limitant de façon quelconque l'invention. The invention will now be described more fully with the aid of the following examples. These cannot be
interpreted as limiting the invention in any way.

Exemple 1 : Préparation du bromo-l tétrafluoroéthyloxométhyl-4
benzène

Figure img00040001

par action de BrCF2CF2Br sur
Figure img00040002
Example 1 Preparation of bromo-1 tetrafluoroethyloxomethyl-4
benzene
Figure img00040001

per action of BrCF2CF2Br on
Figure img00040002

Dans un ballon surmonté d'un réfrigérant à carboglace et contenant 400ml de diméthylformamide anhydre dégazé à l'argon, on dissout 14,6g (0,1 mole) de

Figure img00040003

et 0,76g (0,01 mole) de propanethiol à 200C. On ajoute- ensuite goutte à goutte sous agitation 39g (0,15 mole) de BrCF2CF2Br. La température augmente de 20 à 240C. On laisse le mélange sous agitation pendant 1h à 400C, puis 12h à température ambiante. Le solvant et KBr qui se forme au cours de la réaction sont éliminés par addition de 400ml d'eau acidifiée par HCl (à 17 %). L'huile qui décante est récupérée. Après purification par un entratnement à la vapeur d'eau, cette huile est séchee sur carbonate de sodium.In a flask surmounted by a dry ice condenser and containing 400 ml of anhydrous dimethylformamide degassed with argon, 14.6 g (0.1 mol) of
Figure img00040003

and 0.76 g (0.01 mole) of propanethiol at 200C. 39 g (0.15 mole) of BrCF2CF2Br are then added dropwise with stirring. The temperature increases from 20 to 240C. The mixture is left under stirring for 1 hour at 400C, then 12 hours at room temperature. The solvent and KBr which forms during the reaction are removed by adding 400 ml of water acidified with HCl (at 17%). The decanting oil is recovered. After purification by steaming, this oil is dried over sodium carbonate.

On sépare par distillation à la bande tournante 10,9g d'un produit dont le point d'ébullition est Eb30mmHg = 860C et dont l'analyse
RMN du proton et du fluor révèlent la formule

Figure img00040004
10.9 g of a product are separated by rotary band distillation, the boiling point of which is Eb30mmHg = 860C and the analysis of which
Proton and fluorine NMR reveal formula
Figure img00040004

Exemple 2 : Préparation du bromo-l tétrafluoroéthyloxobenzène

Figure img00040005
Example 2 Preparation of bromo-1 tetrafluoroethyloxobenzene
Figure img00040005

<tb> <SEP> OCF2CF2Br
<tb> par <SEP> action <SEP> de <SEP> BrCF2CF2Br <SEP> sur <SEP> OK+.
<tb> <tb><SEP> OCF2CF2Br
<tb> by <SEP> action <SEP> of <SEP> BrCF2CF2Br <SEP> on <SEP> OK +.
<tb>

On opère comme dans l'exemple 1 avec 13,2g (0,1 mole) de

Figure img00050001
The procedure is as in Example 1 with 13.2 g (0.1 mole) of
Figure img00050001

Par distillation à la bande tournante, on sépare 7g d'un produit dont le point d'ébullition est Eb40mmHg 760C et dont l'analyse
RMN du proton et du fluor révèlent la formule

Figure img00050002
By rotary band distillation, 7 g of a product are separated, the boiling point of which is Eb40mmHg 760C and the analysis of which
Proton and fluorine NMR reveal formula
Figure img00050002

Exemple 3 : Préparation du bromo-l tétrafluoroéthyloxo chloro-4
benzène

Figure img00050003

par action de BrCF2CF2Br sur
Figure img00050004
Example 3 Preparation of bromo-1 tetrafluoroethyloxo chloro-4
benzene
Figure img00050003

per action of BrCF2CF2Br on
Figure img00050004

On opère comme dans l'exemple 1 avec l6,6g (0,1 mole) de

Figure img00050005
The procedure is as in Example 1 with 16.6 g (0.1 mole) of
Figure img00050005

Par distillation à la bande tournante, on sépare 5,8 g d'un produit dont le point d'ébullition est Eb30mmHg = 800C et dont l'analyse RMN du proton et du fluor révèlent la formule

Figure img00050006
By rotary band distillation, 5.8 g of a product are separated, the boiling point of which is Eb30mmHg = 800C and the NMR analysis of the proton and fluorine reveal the formula
Figure img00050006

Exemple 4 : Préparation du bromo-l tétrafluoroéthyloxonitro-4
benzène

Figure img00050007

par action de BrCF2CF2Br sur
Figure img00050008
Example 4 Preparation of bromo-1 tetrafluoroethyloxonitro-4
benzene
Figure img00050007

per action of BrCF2CF2Br on
Figure img00050008

On opère comme dans l'exemple 1 avec 17,7g (0,1 mole) de

Figure img00060001
The procedure is as in Example 1 with 17.7 g (0.1 mole) of
Figure img00060001

Par chromatographie sur plaque de silice (Eluant : benzène), on sépare 2g d'un produit dont le point de fusion est P.F. = 650C et dont l'analyse RMN du proton et du fluor révèlent la formule

Figure img00060002
By chromatography on a silica plate (Eluent: benzene), 2 g of a product are separated, the melting point of which is PF = 650C and the NMR analysis of the proton and of the fluorine reveal the formula
Figure img00060002

Claims (19)

NO21 F F' C1 Br, I, CF3, CONR1R2 et NR1R2 où R1 et R2 identiques ou différents représentent chacun un hydrogène ou un radical alkyle ayant de 1 à 6 atomes de carbone.NO21 F F 'C1 Br, I, CF3, CONR1R2 and NR1R2 where R1 and R2, identical or different, each represent a hydrogen or an alkyl radical having from 1 to 6 carbon atoms. - et R représente au moins un élément choisi parmi le groupe comprenant l'hydrogène, les radicaux alkyle ayant de 1 à 12 atomes de carbone, le radical phényle, les radicaux alkoxy ayant de 1 à 12 atomes de carbone, le radical phényloxy et les radicaux  - And R represents at least one element chosen from the group comprising hydrogen, the alkyl radicals having from 1 to 12 carbon atoms, the phenyl radical, the alkoxy radicals having from 1 to 12 carbon atoms, the phenyloxy radical and the radicals - X3 représente Br ou I - X3 represents Br or I - X1 et X2 identiques ou différents représentent F ou Cl - X1 and X2 identical or different represent F or Cl dans laquelle in which
Figure img00070001
Figure img00070001
 REVENDICATIONS 1. Fluorohaloéthyléthers aromatiques de formule CLAIMS 1. Aromatic fluorohaloethyl ethers of formula 2. Fluorohaloéthyléthers aromatiques selon la revendication 1 caractérisés en ce que dans la formule I, X1 et X2 représentent F 2. Aromatic fluorohaloethyl ethers according to claim 1 characterized in that in formula I, X1 and X2 represent F 3. Fluorohaloéthyléthers aromatiques selon l'une quelconque des revendications précédentes caractérisés en ce que dans la formule I, X3 représente Br. 3. Aromatic fluorohaloethyl ethers according to any one of the preceding claims, characterized in that in formula I, X3 represents Br. 4. Fluorohaloéthyléther selon les revendications 2 et 3 caractérisé en ce qu'il répond a la formule 4. Fluorohaloethyl ether according to claims 2 and 3 characterized in that it corresponds to the formula
Figure img00070002
Figure img00070002
 5. Fluorohaloéthyléther selon les revendications 2 et 3 caractérisé en ce qu'il répond à ta formule 5. Fluorohaloethyl ether according to claims 2 and 3 characterized in that it meets your formula
Figure img00070003
Figure img00070003
Figure img00070004
Figure img00070004
 6.Fluorohaloethyléther selon les revendications 2 et 3 caractérisé en ce qu'il répond à la formule 6.Fluorohaloethyléther according to claims 2 and 3 characterized in that it corresponds to the formula 7. Fluorohaloéthyléther selon les revendications 2 et 3 caractérisé en ce qu'il répond à la formule 7. Fluorohaloethyl ether according to claims 2 and 3 characterized in that it corresponds to the formula
Figure img00080001
Figure img00080001
 8. Procéde pour la préparation de composés selon l'une quel-conque des revendications précédentes caractérisé en ce que l'on fait réagir le composé de formule X4-CFX1-CFX2-X3 (II) avec un phenate de formule : 8. Process for the preparation of compounds according to any one of the preceding claims, characterized in that the compound of formula X4-CFX1-CFX2-X3 (II) is reacted with a phenate of formula:
Figure img00080002
Figure img00080002
 où X1, X2, X3 et R ont la signification précédente, M+ représente un cation dérivé d'un metal alcalin, et X4 représente Cl, Br ou I dans un solvant aprotique polaire anhydre en présence d'un thiol agissant comme initiateur de la réaction. where X1, X2, X3 and R have the previous meaning, M + represents a cation derived from an alkali metal, and X4 represents Cl, Br or I in an anhydrous polar aprotic solvent in the presence of a thiol acting as initiator of the reaction . 9. Procédé selon la revendication 8 caractérisé en ce que dans la formule II, X3 est Br et X4 est Br ou Cl.  9. Method according to claim 8 characterized in that in formula II, X3 is Br and X4 is Br or Cl. 10. Procédé selon la revendication 8 caractérisé en ce que dans la formule II, X3 est r et X4 est Cl, Br ou I. 10. Method according to claim 8 characterized in that in formula II, X3 is r and X4 is Cl, Br or I. 11. Procédé selon l'une quelconque des revendications 8 à 10 caractérisé en ce que dans la formule III, M represente le cation dérivé du potassium. 11. Method according to any one of claims 8 to 10 characterized in that in formula III, M represents the cation derived from potassium. 12. Procéde selon l'une quelconque des revendications 8 à11 caractérisé en ce que le solvant aprotique polaire est choisi parmi le groupe comprenant le diméthylformamide, le diméthylsulfoxyde, l'hexaméthylènephosphorotriamide, la N-méthylpyrrolidone et le solfolane. 12. Method according to any one of claims 8 to 11 characterized in that the polar aprotic solvent is chosen from the group comprising dimethylformamide, dimethylsulfoxide, hexamethylenephosphorotriamide, N-methylpyrrolidone and solfolane. 13. Procédé selon l'une quelconque des revendications 8 à 12 caractérisé en ce que le solvant est le dimêthylformamide.  13. Method according to any one of claims 8 to 12 characterized in that the solvent is dimethylformamide. 14. Procédé selon l'une quelconque des revendications 8 à 13 caractérisé en ce que le thiol est choisi parmi le groupe comprenant les alcanethiols, les thiophenols et les benzylmercaptans. 14. Method according to any one of claims 8 to 13 characterized in that the thiol is chosen from the group comprising alkanethiols, thiophenols and benzylmercaptans. 15. Procede selon la revendication 14 caractérisé en ce que le thiol est le propanethiol. 15. Method according to claim 14 characterized in that the thiol is propanethiol. 16. Procédé selon l'une quelconque des revendications 8 à 15 caractérisé en ce que le rapport molaire du thiol au phénate est compris entre environ 0,05 et environ 0,2. 16. Method according to any one of claims 8 to 15 characterized in that the molar ratio of thiol to phenate is between approximately 0.05 and approximately 0.2. 17. Procédé selon l'une quelconque des revendications 8 à 16 caractérisé en ce que le rapport molaire du composé Il au composé 17. Method according to any one of claims 8 to 16 characterized in that the molar ratio of compound II to the compound III est compris entre environ 1 et environ 5.III is between about 1 and about 5. 18. Procédé selon l'une quelconque des revendications 8 à 17 caractérisé en ce que le nombre de mole de phénate par litre de solvant est compris entre environ 0,1 et environ 0,5. 18. Method according to any one of claims 8 to 17 characterized in that the number of moles of phenate per liter of solvent is between approximately 0.1 and approximately 0.5. 19. Procédé selon l'une quelconque des revendications 8 à 18 caracterise en ce que l'on opère a unetempérature comprise entre environ 20 et environ 1000C sous pression atmosphérique.  19. A method according to any one of claims 8 to 18 characterized in that one operates at a temperature between about 20 and about 1000C under atmospheric pressure.
FR8110319A 1980-11-13 1981-05-25 Bromo-poly:fluoro alkyl phenyl ether(s) - intermediates for pharmaceuticals and plant protection agents are prepd. by reacting the phenate with di:bromo-poly:fluoro-methane or ethane Granted FR2506300A1 (en)

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FR8110319A FR2506300A1 (en) 1981-05-25 1981-05-25 Bromo-poly:fluoro alkyl phenyl ether(s) - intermediates for pharmaceuticals and plant protection agents are prepd. by reacting the phenate with di:bromo-poly:fluoro-methane or ethane
EP81401771A EP0052558B1 (en) 1980-11-13 1981-11-06 Aromatic bromopolyfluoroalkyl ethers, and process for their preparation
DE8181401771T DE3166515D1 (en) 1980-11-13 1981-11-06 Aromatic bromopolyfluoroalkyl ethers, and process for their preparation

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Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 81, no. 17, 28 Octobre 1974, page 474, ref. 104876d, Columbus, Ohio, US, V.E. PLATONOV et al.: "Copyrolysis of pentafluorophenol with tetrafluoro-ethylene and bromine" & & Izv. Akad. Nauk. SSSR, Ser. Khim. 1974, (7), 1668-9 *
TETRAHEDRON LETTERS, vol. 22, no. 4, 1981, Pergamon Press Ltd., GB, I. RICO et al: "Synthèse de Composés Aromatiques comportant les Groupements OCF2Br et SCF2BR. I. Action du dibromodifluoromethane sur les thiophénate et phénate de potassium", pages 323-326 *
THE JOURNAL OF ORGANIC CHEMISTRY, vol. 44, no. 16, 3 août 1979, American Chemical Society, A.E. FEIRING: "Chemistry in Hydrogen Fluoride. 7. A Novel Synthesis of Aryl Trifluoromethyl Ethers", pages 2907-2910 *

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